EP0277843A2 - Ozon adsorbierendes und zerstörendes Mittel und Methode für seine Anwendung - Google Patents

Ozon adsorbierendes und zerstörendes Mittel und Methode für seine Anwendung Download PDF

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Publication number
EP0277843A2
EP0277843A2 EP88301002A EP88301002A EP0277843A2 EP 0277843 A2 EP0277843 A2 EP 0277843A2 EP 88301002 A EP88301002 A EP 88301002A EP 88301002 A EP88301002 A EP 88301002A EP 0277843 A2 EP0277843 A2 EP 0277843A2
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EP
European Patent Office
Prior art keywords
ozone
temperature
gas
high silica
ppm
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP88301002A
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English (en)
French (fr)
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EP0277843B1 (de
EP0277843A3 (en
Inventor
Ei Oigo
Mitsuo Maehara
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Union Showa KK
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Union Showa KK
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Publication date
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Publication of EP0277843A3 publication Critical patent/EP0277843A3/en
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Publication of EP0277843B1 publication Critical patent/EP0277843B1/de
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • B01D53/8671Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
    • B01D53/8675Ozone

Definitions

  • the present invention relates to an ozone adsorbing and decomposing agent, more particularly to an ozone adsorbing and decomposing agent which can be suitably used for removing ozone from, for example, ozone-containing air discharged from a wastewater treatment process using ozone, and to a method of using same.
  • the general purpose zeolite has a high ozone decomposing ability when active, the zeolite is highly hydrophilic but the activity thereof is remarkably lowered by moisture adsorption, and thus a problem arises in that it can not be used in a system with a high moisture content.
  • an amorphous inorganic oxide such as silica gel is also hydrophilic, but has a problem of a low activity.
  • most metal oxide catalysts have a problem in that they are deactivated by, for example, water or carbon dioxide.
  • the objects of the present invention are to eliminate the above-mentioned disadvantages of the prior art and to develop an ozone adsorbing and decomposing agent which can effectively remove ozone from a gas with a relatively high water content by solving the problems in the methods of removing ozone in a gas of the prior art as described above, namely the reaction of activated charcoal with ozone, and inability to effectively remove ozone by adsorption or decomposition due to the hydrophilic nature of the conventional zeolites in a system with a high moisture content.
  • an ozone adsorbing and decomposing agent comprising a crystalline zeolite represented by the formula (I):
  • a method for decomposing ozone which comprises treating an ozone-containing gas with an ozone adsorbing and decomposing agent comprising a crystalline zeolite represented by the formula (I):
  • the method for removing ozone by using a conventional zeolite is known in the art, but because the prior art method uses a zeolite molecular sieve which is a crystalline aluminosilicate as the decomposing agent, it is highly hydrophilic and problems arise when it is used in a system containing moisture, as described above.
  • the present inventors made an investigation into the development of an adsorbing agent capable of effectively adsorbing and removing ozone with a high activity even in a system containing water, and consequently, found that ozone could be removed by adsorption and decomposition by using a high silica zeolite represented by the above formula (I), without a substantial lowering of activity even in a system containing moisture.
  • the ozone adsorbing and decomposing agent according to the present invention is represented by the above-mentioned formula (I), and such a high silica zeolite is known in the art, typically as disclosed in Japanese Unexamined Patent Publication (Kokai) No. 54-72795, or is commercially sold under the trade name of Silicalite from Union Carbide Co.
  • Khokai Japanese Unexamined Patent Publication
  • Silicalite from Union Carbide Co.
  • no description is given in any prior art, including the above Publication, that can teach those skilled in the art that a high silica zeolite has extremely effective properties of ozone removal by adsorption and decomposition.
  • the high silica zeolite of the above formula (I) does not exhibit remarkable ion-exchange characteristics, different from the crystalline aluminosilicate generally known as a zeolite molecular sieve, and in further contrast to the conventional zeolite molecular sieve which exhibits a strong hydrophilic property and is used for high degree drying of a fluid, the high silica zeolite exhibits a water repellent and hydropholic property.
  • high silica zeolites preferable for the object of the present Invention are those In which M is a hydrogen ion, ammonium ion, an alkali metal ion such as Na or K, an alkaline earth metal ion such as Ca or Mg, x is 0 to 2, y > 20, and z is 0 or a positive number, preferably 0 to 10, more preferably 2 to 4.
  • the high silica zeolite can be synthesized by the method described in, for example, the above-mentioned Japanese Unexamined Patent Publication (Kokal).
  • a particularly preferably high silica zeolite has a specific gravity of 1.99 ⁇ 0.05 g/cc at 25° C when synthesized as such, a specific gravity of 1.70 ⁇ 0.05 g/cc after calcination (at 600° C in air for one hour), and average refractive indices of 1.48 ⁇ 0.01 and 1.39 ⁇ 0.01, respectively.
  • the high silica zeolite according to the present invention can retain the adsorbed ozone without decomposition at a relatively low temperature (e.g., -10 to +20° C), it can be used as an ozone storage vessel. For example, by placing a high silica zeolite system having ozone adsorbed thereon under a reduced pressure, or by flowing a carrier gas such as oxygen or air through a gas inlet, the adsorbed ozone can be recovered. On the other hand, at a relatively higher temperature (e.g., about 28.5 to 50°C), the adsorbed ozone is decomposed and, therefore, ozone can be effectively removed from, for example, an exhaust gas containing ozone treatment facilities. Further, as mentioned above, since the activity of the high silica zeolite will not be substantially lowered by moisture, even when moisture is contained in the exhaust gas, the ozone can be effectively removed.
  • a relatively higher temperature e.g., about 28.5 to 50°C
  • a special method is not required, and a general method can be practiced by, for example, filling the high silica zeolite into an ozone adsorbing vessel, introducing an ozone containing gas through the inlet at the lower part of the adsorbing vessel, passing the gas through the filled bed of high silica zeolite, and discharging the gas through the upper part of the vessel.
  • the decomposition of ozone in a gas according to the present invention can be effected by using the ozone adsorbing and decomposing agent comprising the high silica zeolite according to the present invention at a temperature of 40° C or more, preferably 45 to 70° C, in any conventional manner known in the art.
  • the ozone contained in the gas discharged from a drinking water treatment process can be fed by a blower to a decomposition vessel filled with the high silica zeolite after heating to a temperature of 40° C or more, and the ozone can be completely decomposed and discharged into the air.
  • a specific feature according to the present invention is that the ozone containing discharged gas can be introduced as such without preliminary drying, and further, the ozone generated from electrical Instruments, including, for example, electrical instruments for domestic use, can be made 0.1 ppm (V) or less.
  • the high silica zeolite according to the present invention for preservation or storage, for example, this can be accomplished by packing the high silica zeolite in a vessel made of stainless steel provided with, for example, a gas Introduction pipe, a gas discharging pipe, a gas distributor, a wire mesh screen, and an rupture disc, and allowing ozone gas to be adsorbed thereon.
  • a vessel made of stainless steel provided with, for example, a gas Introduction pipe, a gas discharging pipe, a gas distributor, a wire mesh screen, and an rupture disc, and allowing ozone gas to be adsorbed thereon.
  • a cylindrical stainless steel vessel having an Inner volume of 3 liters is filled with 2 kg of Silicalite (high silica zeolite produced by Union Carbide) 10 x 60 mesh product
  • about 14 g of ozone can be stored under normal pressure at 20° C.
  • the ozone thus stored can be recovered by, for example, passing air or oxygen through a gas discharging pipe.
  • the temperature of the adsorbent layer during the test was measured by a thermometer inserted to a depth of 46 mm from the inlet end of the above high silica zeolite packing pipe, and the ozone concentration was measured by a DAS1B1 MODEL DY-1500.
  • the ozone concentration in the outlet gas became 650 ppm (V) at 30° C, 200 ppm (V) at 35° C, and 0 ppm (V) at 40° C.
  • An aluminum pipe having an inner diameter of 18.5 mm, an outer diameter of 22 mm, and a height of 553 mm was filled with 70 ml of the above Silicalite pellets, and the test was conducted by introducing an ozone-oxygen gas mixture with an ozone gas concentration of 500 ppm (V) therein, as described in Example 1, at a flow rate of 2 liter/min.
  • Example 1 an aluminum pipe having an inner diameter of 18.5 mm, an outer diameter of 22 mm and a height of 553 mm was filled with 58 g of pellets having a representative diameter of 1.6 mm and a representative length of 1.2 mm, and ozonized air was introduced by feeding a starting air having a relative humidity of RH 430/0 at 17° C without drying into an ozone generator.
  • the ozone concentration at this time was from 575 ppm (V) to 650 ppm (V).
  • the ozone concentration at the pipe outlet when the temperature of the ozonized air was 16.2°C was 500 to 510 ppm, but when the packed layer temperature was gradually elevated by heating with a mantle heater, the ozone concentration In the outlet gas became 0 ppm (V) at a layer temperature of 51.1°C.
  • Figure 3 shows the relationship between the inner layer temperature and the ozone concentration.
  • Example 2 The same stainless steel pipe as used in Example 1 was packed with 325.8 g of high silica zeolite produced by Union Carbide Corp. having a representative diameter of 10 x 60 mesh (trade name: Silicalite), and then three gas humidifying bottles containing 450 g of water at 16° C were connected in series thereto, and oxygen was introduced therein through a pressure reduction valve, from an oxygen bomb, and saturated with water, followed by ozonization by an ozonizer produced by Chiyoda Medics Co. At this time, to prevent condensation of the water, the ozonizer outlet temperature was made 35°C by controlling the cooling of the ozonizer.
  • the gas mixture containing ozone-oxygen-water generated from the ozonizer was introduced into the above Silicalite in the pipe, and while the mixture was heated by a mantle heater, the relationship between the change in the concentration of the ozone and the temperature was measured.
  • the ozone concentration in the Silicalite in the pipe at this time was from 2730 ppm (V) to 2840 ppm (V).
  • the relationship between the filling layer temperature and the ozone concentration at the outlet is shown in Fig. 4.
  • Example 4 an aluminum pipe having an inner diameter of 18.5 mm, an outer diameter of 22 mm ; and a height of 553 mm was packed with 55.2 g of pellets having a representative diameter of 1.6 mm and a representative length of 1.1 mm of the conventional synthetic Na-form-X zeolite (product name: 13X, produced by Union Showa K.K.) to which was previously loaded 4.6 g of water per 100 g of the adsorbent. When 4 liter/min.
  • a stainless steel pipe having a nominal diameter of 21/2 inches (21/2B) and a length of 300 mm was packed with 130 g of a high silica zeolite having a representative particle size of 10 x 60 mesh produced by Union Carbide Co. (trade name: Silicalite).
  • an ozone-oxygen mixture generated by an ozonizer produced by Chiyoda Medics Co. was introduced into this pipe at a flow rate of 2 liter/min., and the ozone adsorbing ability and desorbing ability of Silicalite were measured.
  • the temperature of the adsorbent layer during the test was measured by a thermometer inserted to a depth of 46 mm from the inlet end of the above-mentioned Silicalite packing pipe. The temperature during the measurement was 22.0 to 22.3° C.
  • the ozone concentration was measured by a DAS1B1 MODEL DY-1500.
  • Table 2 and Table 3 are also shown in the graph in Fig. 6.
  • the adsorption amount of 0 3 in this test was calculated to be 0.17 g, while the ozone amount desorbed was calculated to be 0.11 g by graphical integration.

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  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Separation Of Gases By Adsorption (AREA)
  • Treating Waste Gases (AREA)
EP19880301002 1987-02-05 1988-02-05 Ozon adsorbierendes und zerstörendes Mittel und Methode für seine Anwendung Expired EP0277843B1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP23506/87 1987-02-05
JP2350687 1987-02-05
JP167822/87 1987-07-07
JP62167822A JPS644220A (en) 1987-02-05 1987-07-07 Adsorbing and decomposing agent of ozone and usage thereof

Publications (3)

Publication Number Publication Date
EP0277843A2 true EP0277843A2 (de) 1988-08-10
EP0277843A3 EP0277843A3 (en) 1988-09-28
EP0277843B1 EP0277843B1 (de) 1992-11-25

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP19880301002 Expired EP0277843B1 (de) 1987-02-05 1988-02-05 Ozon adsorbierendes und zerstörendes Mittel und Methode für seine Anwendung

Country Status (3)

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EP (1) EP0277843B1 (de)
JP (1) JPS644220A (de)
DE (1) DE3876107T2 (de)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0387044A1 (de) * 1989-03-07 1990-09-12 Sakai Chemical Industry Co., Ltd., Katalysator und Verfahren für die Zersetzung von Ozon
EP0901815A1 (de) * 1997-09-10 1999-03-17 Basf Aktiengesellschaft Katalysator in Tablettenform
US5951957A (en) * 1996-12-10 1999-09-14 Competitive Technologies Of Pa, Inc. Method for the continuous destruction of ozone
EP0948996A3 (de) * 1998-04-03 1999-10-27 Mitsubishi Heavy Industries, Ltd. Ozonadsorptionsmittel, Formteil zur Adsorption von Ozon und Verfahren zu dessen Herstellung
DE102010003880A1 (de) 2010-04-12 2011-10-13 Durtec Gmbh Mineralische Gasadsorber zur Beseitigung von Ozon aus Abluft/Abgas, Verfahren zu deren Herstellung und Regenerierung

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5462905A (en) * 1992-08-21 1995-10-31 Toyota Jidosha Kabushiki Kaisha Exhaust gas purifying catalyst
JPH0929093A (ja) 1995-07-21 1997-02-04 Toyota Central Res & Dev Lab Inc 排ガス浄化用触媒及びその製造方法
JP7221057B2 (ja) * 2019-01-09 2023-02-13 株式会社荏原製作所 窒素酸化物を含むガスの処理装置、および処理方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4101296A (en) * 1975-04-17 1978-07-18 W. R. Grace & Co. Ozone decomposition and electrodesorption process
JPS53108890A (en) * 1977-03-04 1978-09-22 Teruo Takei Catalyst and method for decomposing ozone gas
JPS5547202A (en) * 1978-09-29 1980-04-03 Osaka Oxgen Ind Ltd Treating method for ozone contained in gas
BR8000226A (pt) * 1979-01-15 1980-10-07 Mobil Oil Corp Zeolito zsm-11, processo para sua preparacao, e processo para conversao de uma carga organica

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0387044A1 (de) * 1989-03-07 1990-09-12 Sakai Chemical Industry Co., Ltd., Katalysator und Verfahren für die Zersetzung von Ozon
US5951957A (en) * 1996-12-10 1999-09-14 Competitive Technologies Of Pa, Inc. Method for the continuous destruction of ozone
EP0901815A1 (de) * 1997-09-10 1999-03-17 Basf Aktiengesellschaft Katalysator in Tablettenform
US6521197B1 (en) 1997-09-10 2003-02-18 Basf Aktiengesellschaft Catalytical process of methanol reformation
EP0948996A3 (de) * 1998-04-03 1999-10-27 Mitsubishi Heavy Industries, Ltd. Ozonadsorptionsmittel, Formteil zur Adsorption von Ozon und Verfahren zu dessen Herstellung
US6254962B1 (en) 1998-04-03 2001-07-03 Mitsubishi Heavy Industries, Ltd. Ozone adsorbent, ozone-adsorbing molded product, and method of making same
DE102010003880A1 (de) 2010-04-12 2011-10-13 Durtec Gmbh Mineralische Gasadsorber zur Beseitigung von Ozon aus Abluft/Abgas, Verfahren zu deren Herstellung und Regenerierung
WO2011128073A2 (de) 2010-04-12 2011-10-20 Durtec Gmbh Verwendung von natürlichen mineralischen granulaten als gasadsorber zur beseitigung von gasförmigen schadstoffkomponenten

Also Published As

Publication number Publication date
EP0277843B1 (de) 1992-11-25
DE3876107D1 (de) 1993-01-07
EP0277843A3 (en) 1988-09-28
DE3876107T2 (de) 1993-05-27
JPS644220A (en) 1989-01-09

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